Substantially linear copolymers

ABSTRACT

The invention is directed towards substantially linear copolymers formed using a metal complex having the formula LMX 1 X 2 . L is a bidentate nitrogen-containing ligand with more than 2 nitrogens. M is copper, silver, or gold. X 1  and X 2  are independently selected from the group consisting of halogens, hydride, triflate, acetate, trifluoroacetate, perfluorotetraphenylborate, tetrafluoroborate, C 1  through C 12  alkyl, C 1  through C 12  alkoxy, C 3  through C 12  cycloalkyl, C 3  through C 12  cycloalkoxy, aryl, and any other moiety into which a monomer can insert. Such metal complexes have a tetrahedral or pseudo-tetrahedral structure and may be used with an activating cocatalyst. The invention is derived from polymers and copolymers using such catalyst compositions, especially copolymers having segments formed from olefinic monomers and monomers having at least one hydrocarbyl polar functional group.

This application is a Continuation-In-Part of U.S. Ser. No. 09/212,035filed Dec. 15, 1998 now U.S. Pat. No. 6,037,297 which is aContinuation-in-Part of U.S. Ser. No. 09/991,160 filed Dec. 16, 1997abandoned.

FIELD OF THE INVENTION

The invention is directed towards tetrahedral and pseudo-tetrahedrallate transition metal polymerization catalyst complexes and their use informing homopolymers from olefins or polar monomers and copolymers fromolefins and polar monomers.

BACKGROUND

Polymers and copolymers may be formed from olefinic monomers by usingtransition metal metallocene catalyst technology. This well-knowntechnology uses catalysts containing early transition metal atoms suchas Ti and Zr.

Even though polyolefins formed by such metallocene catalysts possesenhanced properties over polyolefins produced by conventionalZiegler-Natta catalysts, further improvements in properties such aswettability and adhesiveness may be possible. It is believed thatincluding polar monomers in an olefinic polymer or copolymer wouldimprove wettability and adhesiveness in those materials. Unfortunately,polar monomers tend to poison early transition metal catalysts.

Certain late transition metal complexes of palladium and nickelincorporate some polar monomers. However, such catalyst systems arecostly. Also, the polymers so produced are highly branched (85-150branches/1000 carbon atoms) and the functionalities are not in the chainbut at the ends of branches. Consequently, they are limited to polarmonomer contents≦about 15 mol%. Another disadvantage of these systems isthat they incorporate only a limited number of polar monomers (e.g.alkyl acrylates and vinyl ketones). Methyl methacrylate and n-butylvinyl ether are mildly inhibiting or inert.

Certain functional ethylene copolymers can also be made by free radicalpolymerization. In commercial practice, these materials also havesignificant short-chain and some long-chain branching (E. F. McCord, W.H. Shaw, Jr. and K A. Hutchinson, Macromolecules, 1997, 30, 246-256).Furthermore, some functional monomers (e.g. n-butyl vinyl ether) do notreadily incorporate under free radical conditions (K. W. Doak,Encyclopedia of Polymer Science and Technology, 2nd Ed. H. F. Mark, EdJohn Wiley and Sons, New York, 1986, Vol. 6, pp 387-429.

Consequently, there remains a need for a polymerization catalyst capableof forming olefinic polymers and copolymers and that are effectivepolymerization catalysts in the presence of polar monomers.

SUMMARY OF THE INVENTION

In one embodiment, the invention is a substantially linear copolymerrepresented by the formula:

where A is a segment derived from an acyclic aliphatic olefin of 2 toabout 20 carbon atoms;

R is H or CH₃;

X is —OR¹ or —COOR¹;

R¹ is an alkyl group of 1 to 24 carbon atoms; and Y is from about 0.02to about 0.95

DETAILED DESCRIPTION OF THE INVENTION

One embodiment of the invention comprises comprises a substantiallylinear copolymers having the formula:

where A is a segment derived from an acyclic aliphatic olefin of 2 toabout 20 carbon atoms; R is H or CH₃; x is —OR¹ or —COOR¹; R¹ is analkyl group of 1 to 24 carbon atoms and y is from about 0.02 to about0.95 and preferably y is from about 0.18 to about 0.85.

These copolymers have polar functional monomer segments,

which are substantially in the chain rather than at ends of branches.

In the case where —A— is a polymer segment derived from ethylene, thebranch content of which is below about 15 branches/1000 carbon atoms,for example from about 0.5 to less than 15 branches.

In another embodiment, the invention comprises a substantially linearcopolymer having a polymer chain of the formula:

where A is a segment derived from an acyclic aliphatic olefin of 2 toabout 20 carbon atoms. R is H or CH₃. X is —OR¹ or —COOR¹. R¹ is analkyl group of 1 to about 24 carbon atoms and y is from 0.18 to 0.85.

In yet another embodiment, the invention comprises a substantiallylinear copolymer having a polymer chain comprising the formula:

where A is a segment derived from ethylene. R is H or CH₃. X is —OR¹ or—COOR¹. R¹ is an alkyl group of 4 carbon atoms and y is from 0.18 to0.85.

In another embodiment, the invention comprises a substantially linearcopolymer having a polymer chain comprising the formula:

wherein y 0.02-0.95.

In another embodiment, the invention comprises a substantially linearcopolymer having a polymer chain comprising the formula:

wherein y=0.02-0.95.

In another embodiment, the invention comprises a substantially linearcopolymer having a polymer chain comprising the formula:

wherein y=0.02-0.95.

In another embodiment, the invention comprises a substantially linearcopolymer having a polymer chain comprising the formula:

wherein y=0.02-0.95.

The catalyst used in the process to form this invention is a complexhaving the formula LMX₁X₂, wherein L is a nitrogen-containing bidentateligand represented by the formula:

[AZA′]

and

[AA′],

wherein A and A′ are independently selected from the group consisting of

wherein R1 is independently selected from the group consisting ofhydrogen, C₁ through C₁₂ straight chain or branched alkyl, C₃ throughC₁₂ cycloalkyl, aryl, and trifluoroethane;

R2 and R3 are independently selected from the group consisting ofhydrogen, C₁ through C₁₂ straight chain or branched alkyl, C₃ throughC₁₂ cycloalkyl, C₁ through C₁₂ alkoxy, F, Cl, SO₃, C₁ through C₁₂perfluoroalkyl, and N(CH₃)₂;

Z is selected from the group consisting of non-substituted C₁ throughC₁₂ straight chain or branched alkyl, C₃ through C₁₂ cycloalkyl;methoxy; amino; halo; and C₁ through C₁₂ haloalkyl substituted straightchain or branched alkyl or cycloalkyl of up to 12 carbon atoms or C₁-C₄₀aryl or alkylaryl groups.

X₁ and X₂ are independently selected from the group consisting halogens,hydride, triflate, acetate, trifluoroacetate, tris([perfluorotetraphenyl) borate, and tetrafluoro borate, C₁ through C₁₂straight chain or branched alkyl or alkoxy, C₃ through C₁₂ cycloalkyl orcycloalkoxy, and aryl or any other ligand with which a monomer caninsert;

Accordingly, some of the ligands of the present invention have thestructures:

For compactness, some bonds are shown without termination; these bondsare terminated by methyl groups.

The metal M is selected from Cu, Ag, and Au. Among Cu, Ag, and Au, Cu ispreferred; among X₁ and X₂, halogens are preferred.

Suitable non-halide X₁ and X₂ include triflate, tifluoroacetate, trisperfluorotetraphenyl borate, or tetrafluoro borate, hydride, alkylgroups or any other ligand into which a monomer can insert. Among themetal complexes of the present invention, those having the1,1′bis(1-methylbenzimidazol-2yl)1″ methoxyethane ligand or the3,3′(1-ethylbenzimidazol-2yl) pentane ligand, or2,2′bis[2-(1-alkylbenzimidazol-2yl)] biphenyl, where the alkyl group isfrom C₁-C₂₀, and X₁ =X₂=chloride are particularly preferred.

1,1′bis(1-methylbenzimidazol-2yl)1″ methoxyethane ligands with copper asthe metal and chlorine as X₁ and X₂ have the structure

3,3′(1-ethylbenzimidazol-2yl) pentane ligands with copper as the metaland chlorine as X₁ and X₂ have the structure

2,2′bis[2-(1-alkylbenzimidazol-2yl)]biphenyl ligands with copper as themetal and chlorine as X₁ and X₂, and C₁-C₂₀ as R₁, have the structure

Advantageously, the catalysts used to form the present invention are notpoisoned by compounds containing hydrocarbyl polar functional groupswhen used in the formation of polymers and copolymers synthesized all orin part from olefinic monomers. As such, the catalysts of the presentinvention are useful in preparing polymers and copolymers formed fromolefinic monomers, such as polyethylene; polymers and copolymers formedfrom monomers containing hydrocarbyl polar functional groups such aspoly(methyl methacrylate); and copolymers derived from olefins andmonomers containing hydrocarbyl polar functional groups such as poly(ethylene-co-methyl methacrylate).

A process used to form the present invention employs a metal complexhaving the formula LMX₁X₂, (wherein L, M, X₁, and X₂ are as previouslydefined) in combination with an activating cocatalyst. Examples of suchactivating cocatalysts include aluminum compounds containing an Al—Obond such as the alkylalumoxanes such as methylalumoxane (“MAO”) andisobutyl modified methylalumoxane “dry” MAO; aluminum alkyls; aluminumhalides; alkylaluminum halides; Lewis acids other than any of theforegoing list; and mixtures of the foregoing can also be used inconjunction with alkylating agents, such as methyl magnesium chlorideand methyl lithium. Examples of such Lewis acids are those compoundscorresponding to the formula: R″″₃B, or R₃″″Al wherein R″″ independentlyeach occurrence is selected from hydrogen, silyl, hydrocarbyl,halohydrocarbyl, alkoxide, aryloxide, amide or combinations thereof,said R″″ having up to 30 nonhydrogen atoms.

It is to be appreciated by those skilled in the art, that the aboveformula for the preferred Lewis acids represents an empirical formula,and that many Lewis acids exist as dimers or higher oligomers insolution or in the solid state. Other Lewis acids which are useful inthe catalyst compositions of this invention will be apparent to thoseskilled in the art.

Other examples of such cocatalysts include salts of group 13 elementcomplexes. These and other examples of suitable cocatalysts and theiruse in organometallic polymerization are discussed in U. S. Pat. No.5,198,401 and PCT patent documents PCT/US97/10418 and PCT/US96/09764,all incorporated by reference herein.

Preferred activating cocatalysts include trimethylaluminum,triisobutylaluminum, methylalumoxane, alkyl modified alumoxanes, “dry”aliumoxanes, chlorodiethyaluminum, dichloroethylaluminum, triethylboron,trimethylboron, triphenylboron and halogenated, especially fluorinated,triaryl boron and aluminum compounds, carboranes and halogenatedcarboranes.

Most highly preferred activating cocatalysts include triethylaluminum,methylalumoxane, and fluoro-substituted aryl boranes and borates such astris(4-fluorophenyl)boron, tris(2,4-difluorophenylboron),tris(3,5-bis(trifluoromethyl-phenyl) boron, tris(pentafluorophenyl)boron, pentafluorophenyl-diphenyl boron, and bis(pentafluorophenyl)phenylboron and tetrakis (pentafluorophenyl) borate. Suchfluoro-substituted arylboranes may be readily synthesized according totechniques such as those disclosed in Marks, et al., J. Am. Chem. Soc.,113, 3623-3625 (1991). Fluorinated tetraaryl borates or aluminates andperfluoro tetranapthyl borates or aluminates, are also well known in theart.

The catalyst can be utilized by forming the metal complex LMX₁X₂ andwhere required combining the activating cocatalyst with the same in adiluent. The preparation may be conducted in the presence of one or moreaddition polymerizable monomers, if desired. Preferably, the catalystsare prepared at a temperature within the range from −100° C. to 300° C.,preferably 0° C. to 250° C., most preferably 0° C. to 100° C. Suitablesolvents include liquid or supercritical gases such as CO₂, straight andbranched-chain hydrocarbons such as isobutane, butane, pentane, hexane,heptane, octane, and mixtures thereof; cyclic and alicyclic hydrocarbonssuch as cyclohexane, cycloheptane, methylcyclohexane,methylcycloheptane, halogenated hydrocarbons such as chlorobenzene, anddichlorobenzene perfluorinated C₄₋₁₀ alkanes and aromatic andalkyl-substituted aromatic compounds such as benzene, toluene andxylene. Suitable solvents also include liquid olefins which may act asmonomers or comonomers including ethylene, propylene, butadiene,1-hexene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-octene, 1-decene,and 4-vinycylohexane, (including all isomers alone or in mixtures).Other solvents include anisole, methylcbloride, methylene chloride,2-pyrrolidone and N-methylpyrrolidone. Preferred solvents are aliphatichydrocarbons and aromatic hydrocarbon, such as toluene.

It is believed that the cocatalyst interacts with the catalyst to createa polymerization-active, metal site in combination with a suitablenon-coordinating anion. Such an anion is a poor nucleophile, has a largesize (about 4 Angstroms or more), a negative charge that is delocalizedover the framework of the anion, and is not a strong reducing oroxidizing agent [S. H.

Strauss, Chem. Rev. 93, 927 (1993)]. When the anion is functioning as asuitable non-coordinating anion in the catalyst system, the anion doesnot transfer an anionic substituent or fragment thereof to any cationicspecies formed as the result of the reaction.

The equivalent ratio of metal complex to activating cocatalyst (whereemployed) is preferably in a range from 1:0.5 to 1:10⁴, more preferablyfrom 1:0.75 to 1:10³. In most polymerization reactions the equivalentratio of catalyst:polymerizable compound employed is from 10⁻¹²: to10⁻¹:1, more preferably from 10⁻⁹:1 to 10⁻⁴:1.

The catalysts used to prepare the present invention have a tetrahedralor pseudo-tetrahedral structure. It is believed that this structure ispresent when the catalyst is in the form of an isolated solid compoundand when the catalyst is used in the presence of activating cocatalystsof this invention under homopolymerization or copolymerizationconditions.

Olefinic monomers useful in the forming homo and copolymers with thecatalyst of the invention include, for example, ethylenicallyunsaturated monomers, nonconjugated dienes, and oligomers, and highermolecular weight, vinyl-terminated macromers. Examples include C₂₋₂₀olefins, vinylcyclohexane, tetrafluoroethylene, and mixtures thereof.Preferred monomers include the C₂₋₁₀ α-olefins especially ethylene,propylene, isobutylene, 1-butene, 1-hexene, 4-methyl-1-pentene, and1-octene or mixtures of the same.

Monomers having hydrocarbyl polar functional groups useful in forminghomo and copolymers with the catalyst of the invention, are vinyl etherand C₁ to C₂₀ alkyl vinyl ethers such as n-butyl vinyl ether, acrylates,such as C₁ to C₂₄, or alkyl acrylates such as t-butyl acrylate, andlauryl acrylate, as well as methacrylates such as methyl methacrylate.

In general, the polymerization may be accomplished at conditions wellknown in the prior art for Ziegler-Natta or Kaminsky-Sinn typepolymerization reactions, that is, temperatures from −100° C. to 250° C.preferably 0° C. to 250° C., and pressures from atmospheric to 2000atmospheres (200 Mpa). Suitable polymerization conditions include thoseknown to be useful for metallocene catalyst when activated by aluminumor boron-activated compounds. Suspension, solution, slurry, gas phase orother process condition may be employed if desired. The catalyst may besupported and such supported catalyst may be employed in thepolymerizations of this invention. Preferred supports include alumina,silica, and polymeric supports.

The polymerization typically will be conducted in the presence of asolvent. Suitable solvents include those previously described as usefulin the preparation of the catalyst. Indeed, the polymerization may beconducted in the same solvent used in preparing the catalyst.Optionally, of course, the catalyst may be separately prepared in onesolvent and used in another.

The polymerization will be conducted for a time sufficient to form thepolymer and the polymer is recovered by techniques well known in the artand illustrated in the examples hereinafter. Of course care must beexercised otherwise some of the functional groups may be partiallyhydrolyzed upon work-up.

The invention is further described in the following non-limitingexamples.

EXAMPLES I. CATALYST PREPARATION Example 1

Preparation of 1,1′bis(1-hydrobenzimidazol-2yl)carbinol (HBBIOH)

A mixture of 8.0 g of (66.6 mmol) of hydroxypropanedioic acid and 14.41g (133.3 mmol) of 1,2-phenylenediamine in 90 mL of 4 N hydrochloric acidwas refluxed for 18 h. The reaction mixture was cooled and the pH wasadjusted to about 8 with ammonium hydroxide to give a pale-green solid.The solid was collected by filtration and dried in a vacuum oven to give8.85 g of 1,1′bis(1-hydrobenzimidazol-2yl)carbinol. Yield: (50.3%); mp238° C. (sub1); ¹H NMR (500 MHz, d⁶ DMSO) δ 7.50 (m, 4H), 7.15 (m, 4H),4.70 (s, 1H), 2.55 (s, 1H). In these examples, NMR resonances areidentified as “m” for multiplet and “s” for singlet. IR absorptions aredenoted s for strong, m for medium, and w for weak.

Example 2

Preparation of 1,1′bis(1-methylbenzimidazol-2yl)1″ methoxyethane(MeBBIOMe)

A 1.0 g (3.8 mmol) quantity of HBBIOH was suspended in 50 ml of dry TBF.Under Ar, sodium hydride (80% dispersion in mineral oil, 0.68 g, 22.8mmol) was added to the suspension and was stirred for 0.5 h. A 2.16 g(15.2 mmol) quantity of iodomethane was added dropwise and allowed tostir for 18 h. The reaction mixture was quenched with saturated aqueoussodium sulfate solution. THF was removed by rotory-evaporation. The oilwas washed with water and separated with methylene chloride followed bychromatography. The 1,1′bis(1-methylbenzimidazol-2yl)1″ methoxyethanewas recrystallized from a mixture of 2-propanol and cyclohexane to give0.23 g of solid. Yield 18.9%; mp 194-195° C.; EI-MS 320; ¹H NMR (CDCl₃)δ 2.29 (s, 3H), 3.27 (s, 3H), 3.67 (s, 6H), 7.26-7.36 (m, 6H), 7.79-7.82(m, 2H).

Example 3

Preparation of Cu(MeBBIOMe)Cl₂

A solution of ethanol and triethylorthoformate was prepared by refluxing30 ml of 100% ethanol and 4 ml of triethylorthoformate. A 245 mg (1.82mmol) quantity of CuCl₂ (99.999% Aldrich) was dissolved in theethanol/triethylorthoformate solution to form a yellow-green solution.After the addition of 584 mg (1.82 mmol) of solid MeBBIOMe an intenselyyellow colored crystalline precipitate formed. The complex,[1,1′bis(1-methylbenzimidazol-2yl)1″ methoxyethane] copper(II)dichloride, Cu(MeBBIOMe)Cl₂, was collected by filtration and dried undervacuum. Measurements revealed a melting point (mp) 262-263° C.(decomposition). Elemental analysis calculations predicted relativeconcentrations of C, 50.19 wt %; H, 4.40 wt %; Cl, 15.61 wt %; and Cu,14.00 Wt %. Laboratory measurements found C, 50.11 wt %; H, 4.48 wt %;Cl, 15.87 wt %; and Cu, 14.1 wt %; The X-ray crystallographic structureis shown in FIG. 1; bond angles are N3-Cu1-Cl2 101.7°, N1-Cu1-Cl1104.6°, Cl2-Cu1-Cl1 105.9°, N3-Cu1-Cl1 126.30, N1-Cu1-Cl2 129.60.Accordingly, this compound has a pseudo-tetrahedral structure.

Example 4

Preparation of Cu(tributBBIM)Br₂

A 260 mg (1.16 mmol) quantity of CuBr₂ (99.99% Aldrich) was dissolved in25 mL of ethanol to form an orange-brown solution. After the addition of365 mg (0.88 mmol) of solid 1,1′bis(1-butylbenzimidazol-2yl)pentane,(tributBBIM), prepared by the methods of Examples 1 and 2, using malonicacid, 1,2-phenylene diamine and butyl iodide as the alkylating agent, ared-brown solution formed. Then 1 mL of triethylorthoformate was addedto the solution and filtered. Upon standing the complex,[1,1′bis(1-butylbenzimidazol-2yl)pentanelcopper(II) dibromide,Cu(tributBBIM)Br₂, formed as long thin red prisms. The crystals werecollected by filtration and air dried, mp 215° C. (decomp.). The X-raycrystallographic structure is shown in FIG. 2; bond angles were measuredto be Br1-Cu1-N11 130.6°, N1-Cu1-Br1 106.4°, N11-Cu1-Br2 99.10,Br1-Cu1-Br2 100.50, N1-Cu1-Br2 134.8°. Accordingly, this structure has apseudo-tetrahedral structure.

Example 5

Preparation of (3,3′(1-ethylbenzimidazol-2yl)pentane]copper(II)dichloride, Cu(tetEtBBM)C₁₂ and ditifuoromethylsulfonate,Cu(teEtBBIM)(trif)₂ 3,3′(1-Ethylbenzimidazol-2yl) pentane copper (II)dichloride, Cu(tetEtBIM)Cl₂ was prepared by the Examples 1-3, usingmalonic acid and 1,2 phenylene diamine and ethyl iodide as thealkylating agent. A suspension of 65 mg of[3,3′(1-ethylbenzimidazol-2yl)pentane]copper(II) dichloride,Cu(tetEtBBIM)Cl₂, was prepared in a solution consisting of 35 ml ofmethylene chloride and 0.5 ml of triethylorthoformate. To the stirredsuspension 67.5 mg of silver trifluoromethylsulfonate, Ag(trif), wasadded. After stirring about 15 minutes the solution was filtered. Afterslow evaporation, the filtrate afforded bright blue prisms ofCu(tetEtBIM)(trif)₂ which were collected by filtration. X-raycrystallographic data revealed a=9.8303 Å, b=10.3048 Å, c=16.1909 Å,α=80.3697°, β=72.7137°, γ=71.4988°, Volume=1480.29 Å³.

Example 6

Preparation of 2,2′bis[2-(1-ethylbenzimidazol-2yl]biphenyl] copper(II),Cu(diEtBBIL)Cl₂

A solution of ethanol and triethylorthoformate was prepared by combining35 mL of 100% ethanol and 4 mL of triethylorthoformate. A 500 mg (2.93mmol) quantity of CuCl_(2—2)H₂O (Aldrich) was dissolved to form a greensolution. After the addition of 500 mg (1.13 mmol) of solid diEtBBIL,±2,2′bis[2-(1-ethylbenzimidazol-2yl)]biphenyl, prepared by the method ofExample 1 and 2, using 2,2′-diphenic acid, 1,2-phenylenediamine, andethyl iodide as alkylating agent, the mixture was refluxed for 5minutes. Upon cooling an organe-brown microcystalline solid wasobtained. The solid was collected by filtration, washed withtriethylorthoformate and pentane, then air dried to give 585 mg oforange-brown solid; mp 206-207° C. (decomp). The orange-brown solid wasrecrystallized from hot nitromethane to give the yellow crystallinecomplex, ±2,2′-bis[2-(1-ethylbenzimidazol-2yl)]biphenylcopper(II)dichloride, Cu(diEtBBIL)Cl₂, which was collected by filtration and driedunder vacuum; mp 275° C. (soften) 285° C. (decomp.); Anal. Calcd. Cu,11.01 Found Cu, 11.01; IR(KBr pellet, cm⁻¹)3439 br, 3069 w, 2962 w, 1668s 2947 sh, 2926s, 2852 m, 1465 s, 1418 s, 776 sh, 761 sh, 746 s. X-raycrystallographic data: N1-Cu1-N3 111°; P2(1)2(1), Z=4, a=15.980 Å,c=20.538 Å, α=90°, γ=90°, Volume=5387.36 Å³; solution EPR(toluene/nitromethane) A₁₁=15 Gauss.

Example 7

Preparation of[±2,2′-bis[2-(1-octylbenzimidazol-2yl)]biphenyl]copper(II) dichloride,Cu(diOctBBIL)Cl₂

A 200 mg quantity of CuCl₂·2H₂O (Aldrich) was dissolved in 15 ml ofethanol to give a green solution. Then 100 mg of diOctBBIL, prepared bythe method of Example 1 and 2, using 2,2′-diphenic acid, 1,2phenylenediamine and 1-iodooctane as the alkylating agent, was added asan oil, followed by the addition of 1 ml of triethylorthoformate. Themixture was heated to reflux for 10 min., then allowed to cool. Uponstanding the solution afforded bright-yellow thin plates of[±2,2′-bis[2-(1-octylbenzimidazol-2yl)]biphenyl]copper(II) dichloride.The crystalline solid was collected by filtration and washed withpentane. Yield 110 mg, MP 152-153° C., Elemental Analysis for Cu: calcd8.52; found 8.45; X-ray crystallographic data: space group P-1, Z=2,a=12.152 Å, b=14.099 Å, c=23.253 Å, α=90.18°, β=90.09°, γ=95.29°,Volume=3967.0 Å³.

II. HOMOPOLYMERIZATION AND COPOLYMERIZATION

Reactions were conducted under argon using Schlenk and gloveboxtechniques. All solvents and monomers were purified by standardtechniques, Perrin, D. D., Armarego, W. L F. Purification of laboratoryChemicals; Pergamon: New York, 1988. 30% MAO in toluene, available fromAlbemarle, Inc. (Baton Rouge, La.), was used as received. Generalprocedure for polymer workup: First a sufficient amount of methanol isadded in order to quench the polymerization reaction. Then the mixtureis added to 5 to 10 times its volume of methanol containing 10 ppm of2,6 Di-tertbutyl-4-methylphenol, (BHT), in order to precipitate thepolymer. Then 10 ml of 2 N HCl is added to the mixture containing thepolymer and is soaked for a sufficient time to remove the catalyst andcocatalyst from the polymer. The polymer is generally collected byfiltration and dried under vacuum. “RT” means ambient or roomtemperature, i.e. a temperature from about 20° C. to 26°C.

Example 8

Polyethylene

A glass lined Parr reactor was loaded in an Ar glove box with 14.1 mg(0.024 mmol) of Cu (diEtBBIL)Cl₂ followed by 30 mL of toluene to give apale yellow partially dissolved solution. Next 2.0 mL of 30% MAO wasadded to give a nearly colorless solution. The Parr was sealed and takento a hood containing the controller for the Parr and pressurized with270 psig ethylene and polymerized at 80° C. for ˜24 hours. The reactionwas cooled, vented and quenched with MeOH. The product was collected byfiltration, washed with MeOH and dried at 70° C. for 2 hours.Yield=16.15 g of white polymer. Turnover Number (TON), moles substrateconverted/moles catalyst=24,000. ¹³C NMR (TCE, Cr(AcAc)₃) δ 29.5(s,—CH₂—). There were no detectable resonances for branching elsewhere inthe spectrum, using the method of Randall J. Macromol.Sci., Rev.Macromol. Chem. Phys. C29 (292) 1989. (Branch content<0.5 branches/1000carbon atoms.) The ¹H NMR (TCE) δ 1.3 (s, —CH₂—) δ 0.95 (m, CH₃ endgroups) (δ 4.95-5.10 (m, olefin end groups). The ratio of CH₃ to olefinend groups was>3:1. Polymer M_(η)=4,900, Mw=13,900, by GPC (in TCB);Tm=139.1° C., ΔH=209.8 J/g.

Example 9

Polyethylene Polymerization, Hexane Slurry Conditions

Polymerization was run using a hexane slurry prepared by suspending 3.72mg (0.0082 mmol) of CuMeBBIOMe)Cl₂ in hexane followed by activation with2.5 mL of 10% MAO (0.004 mol). The reactor was pressurized with 125 psigof ethylene and heated to 60° C. for 0.5 h to yield 2.4 g of solidpolyethylene (TON=10,900). Polyethylene Mn=150700, MVVD=2.33 by GPC (inTCE, polyethylene standard). Polymer T_(m)=140° C.

Example 10

Polyethylene Polymerization, Moderate Pressure Conditions

A high-pressure HASTELLOY™ reactor was loaded in an Ar glovebox with aslurry prepared by suspending 35 mg (0.077 mmol) of Cu(MeBBIOMe)Cl₂ in4.0 mL of toluene followed by activation with 1.0 ml of 30% MAO (0.005mol). The reactor was pressurized with 5.6 g (0.20 mol) of ethylene andheated to 80.5° C., resulting in a pressure of 5170 psig. The pressuredropped to 4390 psig over a 2.75 h period indicating an uptake ofethylene. The polymerization mixture was cooled and quenched withmethanol to give 1.1 g of solid polyethylene. (20% yield based onethylene) Polyethylene Mn=145,400, MWD=2.55, Tm=139° C., ΔH_(f)=122 J/g.

Example 11

Polymerization of Ethylene

The polymerization was run using a slurry prepared by suspending 12.8 mg(0.022 mmol) of Cu(diEtBBIL)Cl₂ in 30 mL of toluene and 10 mL of1,2-dichlorobenzene followed by activation with 2.5 ml of 30% MAO togive a yellow suspension. The Parr reactor was pressurized with 500 psigof ethylene and heated to 80° C. and maintained at 80° C. for ½h duringwhich the pressure dropped from 730 psi to 580 psig. The polymerizationmixture was cooled and quenched with methanol to give 7.97 g of solidpolyethylene upon workup (TON=12,700 moles^(PE)/moles catalyst).

Example 12

Polyethylene Polymerization, Toluene Slurry

The polymerization was run using a toluene slurry prepared by suspending20.8 mg (0.029 mmol) of [3,3′(1-ethylbenzimidazol-2yl)pentane]copper(II)ditrifluoromethylsulfonate, Cu(tetEtBBMI)(trif)₂ in 30 mL of toluenefollowed by activation with 2.0 mL of 30% MAO (0.01 mol) to give ayellow suspension. The PARR™ reactor was pressurized with 300 psig ofethylene and heated to 90° C. and further pressurized to 750 psig andmaintained at 90° C. for 20 h during which the pressure dropped to 740psi. The polymerization mire was cooled and quenched with methanol togive 210 mg of solid polyethylene upon workup. Polyethylene Tm=137° C.

Example 13

Copolymerization of Ethylene and 1-hexene

A high-pressure HASTELLOY™ reactor was loaded in an Ar glovebox with aslurry prepared by suspending 30.1 mg (0.066 mmol) of Cu(MeBBIOMe)Cl₂ in2.0 mL of toluene followed by activation with 1.0 mL of 30% MAO (0.005mol). This was followed by the addition of 0.67 g of 1-hexene. Thereactor was pressurized with 4.1 g of ethylene (0.146 mol) and heated to80° C. resulting in a pressure of 850 psig. The pressure dropped to 690psig over a 1.5 h period and the polymerization mixture was cooled andquenched with methanol to give 1.6 g of solid copolymer. (33.5% yieldbased on charge of monomers) Copolymer Mi=133,500, MWD=2.51, Tm=107,123° C.

Example 14

Poly(t-butyl acrylate)

A 20.1 mg (0.044 mmol) quantity of Cu(MeBBIOMe)Cl₂ was added to a 100 mLround-bottomed flask in an Ar glovebox. A 10 mL quantity of toluene wasadded to the flask, followed by 0.11 g of 30 wt. % MAO (0.57 mmol)resulting in an yellow slurry. 7.45 g of t-butyl acrylate (freshlydistilled from CaCl₂ and stabilized with 300 ppm of phenathiazine) wasadded to the slurry. The flask was covered with aluminum foil and themixture was allowed to stir at room temperature for 18 hours in thedark. At the end of this time period, the reaction was quenched with 5mL of methanol and then the polymer was precipitated out in 150 mL ofacidic methanol (10%). The polymer was isolated by filtration and driedunder vacuum at 40° C. for a day. Yield: 57%. Mn=470,000; Mw=851,000;MWD=1.8. ¹³C NMR (ppm, CDCl₃): 28.2 (s, —CH₂—CH(COOC(CH ₃)₃)—),34.3-37.6 (m, —CH₂ —CH(COOC(CH₃)₃)—), 42-43.5 (m, —CH₂—CH(COOC(CH₃)₃)—),80.5 (m, —CH₂—CH(COOC(CH₃)₃)—), 173.2-174.1 (m, —CH₂—CH(COOC(CH₃)₃)—),38% rr, 46% mr, 16% mm (by integration of methine peak).

Example 15

Poly(methyl methacrylate)

19.6 mg of Cu(MeBBIOMe)Cl₂ was added to 5 mL of toluene in a 100 mLround-bottomed flask in an Ar glovebox. To another 5 mL quantity oftoluene, 4.41 g of methyl methacrylate (stabilized with 400 ppm ofphenathiazine) was added, followed by 0.15 g of 30 wt. % MAO (0.78mmol). This pale yellow solution was added to the flask, which wassealed and covered with aluminum foil. The reaction mixture was stirredat room temperature for 16 hours in the dark. At the end of this timeperiod, the green-yellow reaction mixture was quenched with methanol andthen tie polymer was precipitated out in 150 mL of acidic methanol(10%). The polymer was isolated by filtration and dried under vacuum at50° C. for a day. Yield: 51%. M_(n)=140,000; Mw=635,000; MWD=4.6. ¹H NMR(ppm, CDCl₃): 0.86, 1.02, and 1.21 (s, —CH₂—C(CH ₃)(COOCH₃)—), 1.5-2.2(broad m) and 1.91 (s, —CH ₂—C(CH₃)(COOCH₃)—), 3.63 (s,—CH₂—C(CH₃)(COOCH ₃)—), 76% rr, 18% mr, 6% mm (by integration of methylpeaks at 0.8 (rr), 1.0 (mr), 1.2 (mm) ppm).

Example 16

Poly n-butyl Vinyl Ether

In an Ar glovebox a yellow suspension was prepared by adding 1.0 ml of30% MAO to 25 ml of toluene containing 10.2 mg (0.022 mmol) ofCu(MeBBIOMe)Cl₂. Then 5.0 mL n-butyl vinyl ether (44 mmol) was added tothe suspension. The mixture was allowed to stir at RT for 20 h duringwhich time the mixture became a viscous pale red-brown solution. Thepolymerization was quenched with methanol. Upon workup 2.07 g ofamorphous poly n-butyl vinyl ether was obtained Yield: 53%, IR (film,KBr plate, cm⁻¹) 2956 (s), 2930 (s), 2871 (s), 1464 (m), 1457 (m), 1377(m), 1039 (s). ¹H NMR (CDCl₃) δ 0.95 (t, CH₃), 1.3-1.9 (m, CH₂), 3.3-4.7(m, CH—o, —O—Ch₂); ratio δ 0.95-1.9/ δ 3.3-4.7=3H/9H. ¹³C NMR (CDCl₃) δ13.5 (s, CH₃), 19.5 (s, CH₂O, 31.0 (s, CH₂) 39.0-41.0 (m, CH₂), 67.5 (m,—OCH), 73.5 (m, —OCH₂). GPC: Mn=6300, M₂=30,000.

Example 17

Ethylene/t-Butyl Acrylate Copolymer

A Parr reactor was loaded with 33.5 mg (0.0679 mmol) of Cu (tetEtBBIM)Cl₂ followed by 35 mL of toluene, then by 2.0 mL of 30% MAO (0.01moles) in an argon dry box to give a yellow suspension. The 6.0 mL(5.37g) (54 mmol) of t-butyl acrylate was added to give a yellow-greensuspension. The Parr was sealed and set up in a hood and pressurizedwith 750 psig of ethylene and polymerized at 90° C. for 24 hours. Thereaction mixture was cooled and quenched with MeOH. Subsequently, thecontents of the reactor were added to ca 150 mL of MeOH giving a whiteprecipitate. A 10 mg quantity of BHT and 25 mL of HCl were added, andthe mixture was allowed to soak to dissolve catalyst residues. Thepolymer was extracted from the water phase with CH₂Cl₂ and Et₂O. Thesolvents were removed by vacuum and the polymer was dried in a vacuumoven at 55° C. to give 2.96 g of pale-green solid. Catalyst turnovers(TON) (moles substrate converted per mole of catalyst) for t-butylacrylate is 307, for ethylene is 151. ¹HNMR (CDCl₃) δ 0.7-0.85 (m CH₃end groups), δ 1.1-1.25 (m—CH₂—), δ 1.4 (s—O—C(CH₃)₃)), δ 2.05-2.25(broad m,

The presence of a multiplet rather than a triplet at 2.05-2.25 ppm, andthe lack of a resonance at 1.6 ppm is consistent with in chain esterunits rather than ester ended branches, such as —CH₂)_(n)CH₂COOC(CH₃)₃.Integration of the monomer units indicates a copolymer composition of ca67% t-butyl acrylate units and 33% ethylene units. ¹³C NMR (δ, CDCl₃), δ27 ppm (t, CH₃'s of the t-butyl group), δ67 (s,

of t-butyl group), δ 41.5-42.8 (m, —CH₂—), δ 43.8-44.8 (m, —CH₂—), δ46.5 (s, —CH—). Branching analysis of CH₃ (at δ 19.8), Et (at δ 11.6),C₃-C₆ (at δ 14.1) by ¹³C NMR gave≦4.4 CH₃ branches/1000 C atoms, 7.7CH₃CH₂ branches/1000 C atoms, and 5.1 propyl to hexyl branches/1000carbon atoms. GPC (THF, polystyrene calibration, with DRI and UVdetection at 215 nm) of a sample purified through a neutral aluminacolumn to remove MAO and unreacted monomer: Mu=26,200, Mw=34,200. Thepresence of UV activity across the molecular weight distribution is anindication of copolymer formation. DSC (Tg=+4 and no Tm) also confirmscopolymer rather than homopolymers.

Comparative Example 1

A copolymer was prepared following the procedure of Examples 134 of PCTWO96/23010. ¹HNMR (CDCl₃): 2.2(t, —CH₂CO₂C(CH₃)₃, ester ended branches),1.6 (m, CH₂CH₂CO₂C(CH₃)₃, ester ended branches), 1.45 (s, —C(CH₃)₃),0.95-1.45, (m, CH, and other CH₂). 0.75-0.95 (m, CH₃, ends ofhydrocarbon branches or ends of chains). This spectrum shows that theesters are primarily located at the ends of hydrocarbon branches;integration gave 6.7 mole % t-butyl acrylate. ¹³CNMR quantitativeanalysis, branching per 1000 CH₂: Total methyls (74.8); methyl (27.7),Ethyl (15.3), propyl 1.5), butyl (8.6), ≧amyl and end of chains (30.8),—CO₂C(CH₃)₃ ester (43.2). Ester branches —CH(CH₂)_(n)CO₂C(CH₃)₃ as a %of total ester: n≧5 (44.3), n=1, 2, 3, 4 (37.2), n=0 (18.5). GPC (THF,PMMA standard): Mn=6000 Mw=8310 Mw/Mn=1.39.

Example 18

Ethylene/MMA Copolymer

In an Ar glovebox, a Parr reactor was loaded with 26.1 mg (0.055 mmol)or orange Cu (BBIK) Cl₂, followed by 30 mL of toluene, and finally with2.0 mL of 30% MAO (0.010 mol). Then 4.0 mL (3.74 g) (0.0374 mmol) ofmethyl methacrylate, containing 400 ppm of phenathiazine, was added. TheParr reactor was sealed and set up in a hood and pressurized with 750psig of ethylene and polymerized at 90° C. for 19.5 hours. The reactionwas quenched with MeOH. The polymer was collected by filtration to give0.68 g of white polymer. Turnover Number (TON) (moles substrateconverted for mole of catalyst) for MMA=109, for ethylene=50. IR (film,cm⁻¹l) 3441 w, 3001 s, 2951 s, 2943 sh,

1456 (CH₂), 1246 s (C—O), 1149 s (C—O), 1000 sh, 991 s, 914 w, 844 m,812 w, 756 m (CH₂). ¹H NMR (CDCl₃) δ 0.61 (m, CH₃ end groups) δ 0.85-1.1(m, CH₃). δ 1.45-2.45 (m, —CH₂—), δ 3.25-3.35 (s, —OCH₃). Integration of¹H NMR indicates a copolymer composition of 71.3% MMA and 28.7%ethylene. GPC (in TCB, polystyrene calibration): Mn=1,150, Mw=35,900; Tgof polymer−61.2° C. (first heat), no Tm; ¹³C NMR (CDCl₃), δ 18-22 (n,—CH₂—), δ 31-32, δ40-41 (m, —CH₂—), 45.5-46.5 (m,

δ 52.5 (s, —OCH₃), δ 55.8 (m, CH₂—). No backbone methine carbons werefound by a DEPT (Distortionless Enhancement by Polarization Transfer)experiment, indicating no detectable backbone branch sites.

Example 19

Ethylene/n-Butyl Vinyl Ether Copolymer

A Parr reactor was loaded with 33.3 mg (0.0673 mmol) of Cu (tetEBBIM)Cl₂ and 30 mL of toluene, followed by the addition of 2.0 mL of 30% MAO(0.010 mol) to give a yellow suspension. A 5 mL quantity (44 mmol) ofn-butyl vinyl ether was added with no immediate color change. The Parrreactor was sealed and taken to a hood containing the controllers forthe reactor. The reactor was pressurized with 750 psig of ethylene andthe mixture was reacted at 60° C. for 20 hours. The reaction was cooled,quenched and the product was isolated. The polymer was soaked inMeOH/HCl to remove catalyst residues. The product was washed and driedto yield 0.420 g of viscous oil. TON (n-butyl vinyl ether)=61; TON(ethylene)=11.5. IR (film, KBr plate, cm⁻¹) 2958(s), 2931 (s)(CH₂),2872(s), 1465(s), 1458(s), 1377(m), 1093(s), 1039(m), 979(w), 932(w),913(w), 859(w), 802(m) 737(m) CH₂, ¹³C NMR (CDCl₃+CrAcAc)_(3 δ) 13.5 (s,CH₃), 19.5 (s, CH₂) 29.5-30.0 (m, —CH₂—), 31.0(s, CH₂) 39.0-41.5 (m,CH₂), 68.5(m, —CH—O), 73.5 (m, —OCH₂). The presence of the —CH—Oresonance at 68.5 ppm indicates an in-chain copolymer. Integration ofthe NMR indicates a copolymer composition of 84.3% n-butyl vinyl ether,and 15.8% ethylene. The polymer Tg=97, −63° C. with no Tm is consistentwith copolymer formation. GPC polystyrene calibration with DRI and UVdetection at 215 nm), Mn=5390, Mw=23620, Mw/Mn=4.38. The presence of UVactivity across the molecular weight-distribution confirms copolymerformation.

Example 20

Poly(lauryl acrylate)

In a nitrogen glovebox, a polymerization tube was loaded with 17.9 mg(FW 744.5, 2.4×10⁻⁵ mole) of Cu(diOctBBIL)Cl₂ catalyst, followed by20.25 mL of toluene, and finally with 0.8 mL of 10% MAO (0.00138 mole).Then 3.0 g (FW 240.39, 0.0125 mole) of inhibitor free lauryl acrylatewas added. The mixture was allowed to stir at room temperature for 24hours. The yield was 47%, upon workup. ¹³C NMR of the product showedcharacteristic polymer ester peak at 174.4 ppm as against to 166.1 peakfor monomer ester. IR (film, cm⁻⁴) 1736 (polymer ester carbonyl), 1464,1396, 1377, 1258, 1167 and 721. GPC (solvent: THF, polystyrenecalibration) of the product gave Mn 16100 and Mw 69100.

Example 21

Ethylene/Lauryl Acrylate Copolymer

In a nitrogen glove box, a Parr reactor was loaded with 15.0 mg (FW744.5, 2.01×10⁻⁵ mole) of Cu(diOctBBIL)Cl₂ catalyst, followed by 30 mLof toluene, and finally with 2.4 mL of 10% MAO (0.00414 mole). Then 2.0g (FW 240.39, 0.00832 mole) of inhibitor free lauryl acrylate was added.The Parr reactor was sealed and set up in a hood and pressurized with700 psig of ethylene and polymerized at 80° C. for 48 hours. The polymerwas collected by filtration to give 1.3 g of product. Turnover number(TON) (moles of substrate converted for mole of catalyst) for LA=234,for ethylene=306. The ¹³C NMR of the product showed peaks due to bothethylene, as well as lauryl acrylate. Integration of the peak indicatesa copolymer composition of 56.7 mole % ethylene, and 43.3 mole % laurylacrylate. GPC (solvent: THE, polystyrene calibration) of the productgave Mw 7700.

What is claimed is:
 1. A copolymer derived from late transition metalpolymerization having a polymer chain comprising the formula:

where A is a segment derived from an acyclic aliphatic olefin of 2 toabout 20 carbon atoms; R is H or CH₃; X is —OR¹ or —COOR¹, wherein R¹ isan alkyl group of 1 to about 24 carbon atoms; y is from about 0.02 toabout 0.95; and the

group is substantially in the polymer chain, wherein the copolymer issubstantially linear.
 2. The copolymer of claim 1 such that when A is asegment derived from an olefin of 2 carbon atoms, the segment A has abranch content of less than about 15 ethyl or higher branches/1000carbon atoms.
 3. A copolymer derived from late transition metalpolymerization having a polymer chain comprising the formula:

where A is a segment derived from an acyclic aliphatic olefin of 2 toabout 20 carbon atoms; R is H or CH₃; X is —OR¹ or —COOR¹, wherein R¹ isan alkyl group of 1 to about 24 carbon atoms; and y is from 0.18 to0.85, wherein the copolymer is substantially linear.
 4. A copolymerderived from late transition metal polymerization having a polymer chaincomprising the formula:

where A is a segment derived from ethylene; R is H or CH₃; X is —OR¹ or—COOR¹; R¹ is an alkyl group of 4 carbon atoms; and y is from 0.18 to0.85, wherein the copolymer is substantially linear.
 5. A copolymerhaving a polymer chain comprising the formula:

wherein y=0.02-0.95 and the copolymer is substantially linear.
 6. Acopolymer having a polymer chain comprising the formula:

wherein y=0.02-0.95 and the copolymer is substantially linear.
 7. Acopolymer having a polymer chain comprising the formula:

wherein y=0.02-0.95 and the copolymer is substantially linear.
 8. Acopolymer having a polymer chain comprising the formula:

wherein y=0.02-0.95 and the copolymer is substantially linear.
 9. Thecopolymer of claim 1 such that when A is a segment derived from anolefin of 2 carbon atoms, the segment A has a branch content of lessthan about 17 methyl to hexyl branches/1000 carbon atoms.
 10. Acopolymer derived from late transition metal polymerization having apolymer chain comprising the formula:

wherein y=0.02-0.95 and R is an alkyl group of from 1 to about 24 carbonatoms and further wherein the copolymer is substantially linear.
 11. Acopolymer derived from late transition metal polymerization having apolymer chain comprising the formula:

wherein y=0.02-0.95 and R is an alkyl group of from 1 to about 20 carbonatoms and further wherein the copolymer is substantially linear.
 12. Acopolymer derived from late transition metal polymerization having apolymer chain comprising the formula:

wherein y=0.02-0.95 and R is an alkyl group of from 1 to 24 carbon atomsand further wherein the copolymer is substantially linear.
 13. Acopolymer derived from late transition metal polymerization having fromabout 0.02 to about 0.95 of alkyl acrylate segments and the remainingportion being ethylene segments, wherein the copolymer is substantiallylinear.
 14. A copolymer derived from late transition metalpolymerization having from about 0.02 to about 0.95 of methylmethacrylate segments and the remaining portion being ethylene segments,wherein the copolymer is substantially linear.
 15. A copolymer derivedfrom late transition metal polymerization having from about 0.02 toabout 0.95 of alkyl vinyl ether segments and the remaining portion beingethylene segments, wherein the copolymer is substantially linear.